Heat-reactivatable adsorbent gas fractionator and process

ABSTRACT

A process and apparatus are provided for removing a first polar gas from a mixture thereof with a second gas. The gas mixture is passed through a sorbent bed having a preferential affinity for the first polar gas and the first polar gas is sorbed thereon so as to produce a gaseous effluent which has a concentration of first polar gas therein below a predetermined maximum. Then the polar gas sorbed on the sorbent bed is removed therefrom by application of microwave energy, at a temperature at which the sorbent is transparent to such energy, while passing a purge flow of gas in contact with the bed to flush out desorbed first polar gas from the bed. The bed is allowed to cool to a relatively efficient temperature for adsorption. The gas mixture is then again passed in contact with the bed. If two beds are used, one bed can be desorbed while the other is on-stream thereby maintaining a substantially continuous flow of effluent gas. 
     The apparatus of the invention provides a sorbent bed assembly having a microwave energy generator positioned to direct such energy into the sorbent bed for desorption of first polar gas from the bed.

Desiccant dryers have been marketed for many years, and are in wide usethroughout the world. While one desiccant bed is sufficient in manyapplications, it is not capable of supplying a continuous effluent flow.The usual type is made up of two desiccant beds, one of which is on thedrying cycle while the other is being regenerated. The gas to be driedis passed through the desiccant bed in one direction during the dryingcycle, and then, when the desiccant has adsorbed moisture to the pointthat there is no assurance that the moisture level of the effluent gaswill meet the requirements for the system, the influent gas is switchedto the other bed, and the spend bed is regenerated by passing purgeeffluent gas in counterflow therethrough.

The purge gas may be heated before entering the bed, but in the usualsystem, the bed itself is provided with heaters, and the desiccant ineffect baked out to remove the adsorbed moisture. The drying andregenerating cycle are usually equal in duration, and the drying cyclemay be and usually is carried out at a higher gas pressure than theregenerating cycle. Counterflow of the gas purge is used to obtain rapidremoval of the adsorbed moisture with a minimum volume of purge gas.

Such dryers are nearly always inefficient in the use of heat toregenerate the bed, because heat is applied throughout the entiredesiccant bed, all of which is accordingly heated to the sametemperature and for the same length of time, even though the adsorbedmoisture content usually decreases significantly from the point of entryof the influent gas to the point of exit of the dried effluent.Furthermore, because of the high temperature required to regenerate thespent desiccant, the bed acquires a considerable amount of heat duringthe regeneration cycle, and this is necessarily wasted when the bed isperforce cooled down at the start of the drying cycle to a temperatureat which adsorption can proceed efficiently. As is well known, theprocess of adsorption of moisture by a desiccant is accompanied byliberation of heat, and accordingly, the efficiency of adsorption is aninverse function of the temperature.

In accordance with U.S. Pat. No. 3,513,631, patented May 26, 1970, toSeibert and Verrando, Jr., a process for removing moisture from gas isprovided, employing a desiccant bed which on the regeneration cycle isheated to at least 100° C. to remove adsorbed moisture, but theapplication of heat for this purpose is restricted to those portions ofthe bed having a high moisture content, thereby saving time during theregeneration, and also avoiding the waste in application of heat whereit is not required.

The problem with heat-reactivatable adsorbent gas fractionators of thesetypes is that relatively high temperatures of the order of 600° to 650°F. are required in order to drive out the moisture vapor adsorbed on thedesiccant. At such temperatures, the life of the desiccant bed isgreatly shortened, and it may even be possible to remove some water ofhydration with each heat regeneration stage of the cycle, which ofcourse destroys the desiccant.

In a paper entitled The Effect of Regeneration Temperature and Pressureon the Adsorptive Capacity of Silica Gel in a Hydrocarbon Environment,published in FUEL, Volume No. 48(3), by Science and Technology Press,Guildford, Surrey, England in 1969, Kotb and Campbell pointed out thatthe adsorptive capacity of hydrocarbon sorbents decreases with use,rapidly at first, and then more gradually. This degradation results fromdegradation of absorbed hydrocarbons, which leads to deposit of thedegradation byproducts as contaminants on the sorbent, and suchcontaminants of course decrease the adsorptive capacity of the bed.

Moreover, many desiccants such as silica gels undergo chemical orphysical change when held at elevated temperatures, which againinterferes with adsorption. Thus, for example, silica gel whilegenerally considered as amorphous does undergo some structural ordering,referred to as crystallization, at elevated temperatures. Increases oftemperature and pressure produce a more ordered arrangement of themolecule, which reduces surface area, and lowers the adsorptivecapacity. The result can be a shortening of the bed life from severalyears to several months.

In accordance with the present invention, it has been determined thatthe application of microwave energy to desorb a first polar gas andother polar gases adsorbed on a sorbent bed significantly reduces if itdoes not entirely overcome sorbent and sorbed polar gas productdegradation encountered in conventional heat-regeneration systems.Moreover, the application of microwave energy does not damage themolecular structure of the desiccant.

Microwave energy is defined as a radiant form of energy transmitted aselectromagnetic waves having frequencies with the range of about 0.03 toabout 3000 giga Hertz, equivalent to from about 3×10⁷ to about 3×10¹²cycles per second. See U.S. Pat. No. 3,555,693 patented Jan. 19, 1971 toFuter, column 1, line 51. Microwave energy is to be distinguished fromelectrical energy such as the discharge of an electrical currentdirectly through a sorbent or desiccant bed, as described by LowtherU.S. Pat. Nos. 4,038,050 patented July 26, 1977 and 4,094,652 patentedJune 13, 1978, which is not radiant energy.

Most desiccants or sorbents at relatively low temperatures, usually atleast below 500° F., are transparent to microwave energy, andconsequently do not absorb such energy, nor are they heated or activatedby it, except at elevated temperatures, of the order of 2000° to 3000°F. The microwave energy is preferentially absorbed by polar materialsuch as the free water or other material sorbed on the desiccant orsorbent, and this polar material, thus activated, is desorbed. Nonpolarmaterials do not absorb microwave energy. Microwave energy thus absorbedis not available to activate any water of hydration of the desiccant orsorbent until all sorbed material has been desorbed. Removal of thewater of hydration chemically bound to the desiccant or sorbent isundesirable, since it may result in collapse of the molecular structure,which will of course decrease the absorptive capacity. Consequently,application of the microwave energy is halted before water of hydrationis removed, with the result that the desiccant or sorbent is littleaffected by the application of microwave energy.

Moreover, the sorbed water or other sorbed polar material is desorbed ata low temperature, approximately 200° F. Since it is sufficientlyactivated to escape from the sorbent at such low temperatures under theapplication of microwave energy, the sorbent or desiccant need not beheated. Accordingly, the microwave energy can be applied to desiccantsor sorbents having a strongly bound water of hydration, such asmolecular sieves and alumina, which cannot be heated to a highertemperature than this without danger of dehydration. For example, insodium aluminosilicate Na₁₂ [AlO₂)₁₂ (SiO₂)₁₂ ].3H₂ O the water ofhydration is liberated at about 1700° F. In alumina gels Al₂ O₃.0.5H₂ Othe water of hydration is liberated at 1500° to 1600° F. In neither caseis the water of hydration removed by application of microwave energy.

In consequence, the application of microwave energy results innegligible heating of the desiccant itself, since it very likely willnot even reach the water equilibrium temperature of approximately 190°F. at which the free or sorbed water is removed. The result is thatthere is virtually no desiccant damage during regeneration. Moreover,the application of microwave energy gives a much more rapid regenerationthan conventional heat-reactivable adsorbent gas fractionators, and thusthe sorbent beds can be made smaller, with less down-time forregeneration, and a resultant considerable conservation of the energyrequired.

Since there is no need to heat the desiccant bed, there is no need toheat the purge gas. In fact, the purge gas is required only in order toflush out the sorbed polar gas such as water that is desorbed from thesorbent bed, with a considerable saving in the amount of effluent gasrequired for purge. In consequence, smaller sorbent beds operating onfaster regeneration cycles can be used when microwave energy is employedfor regeneration as in the present invention.

In the process of the invention, the concentration of a first polar gasin a mixture thereof with a second gas is reduced to below a limitingmaximum concentration thereof in the second gas by passing the mixturein contact with and from one end to another of a bed of a sorbent havinga preferential affinity for the first polar gas, adsorbing first polargas thereon to form a gaseous effluent having a concentration thereofbelow the maximum, and as the adsorption continues forming aconcentration gradient of first polar gas on the bed progressivelydecreasing from the one end to the other end, and an increasingconcentration of first polar gas in the second gas defining aconcentration front progressively advancing in the bed from the one endto the other end as sorbent capacity therefor decreases; discontinuingpassing the gaseous mixture in contact with the bed before the front canleave the bed, and the limiting maximum concentration of first polar gasin the second gas can be exceeded; and then desorbing the first polargas adsorbed on the sorbent bed by application of microwave energy at atemperature at which the sorbent is transparent to microwave energy,preferably below 500° F., while by passing therethrough a purge gas flowto flush desorbed first polar gas from the bed.

The process is applicable to sorption and desorption of any polar gas inmixtures thereof with other polar or nonpolar gases. Polar gases such aswater, carbon dioxide, carbon monoxide, sulfur dioxide, sulfur trioxide,nitrogen oxides, boron trifluoride, ozone and ethanol are readilydesorbed by microwave energy.

The process contemplates, as the preferred purge gas, gaseous effluentfrom the adsorption cycle, and a desorption at a gas pressure lower thanthat during adsorption, usually from 15 to 350 psi lower, and preferablyat least 50 psi lower.

The advance of the moisture front in a bed of desiccant as it graduallyadsorbs moisture is a well known phenomenon in the desiccant drying art,and is discussed in numerous patents, for example, Skarstrom U.S. Pat.No. 2,944,627. During the greater part of the drying cycle, the sorbentefficiently sorbs moisture from gas passing over it. When the sorbentcapacity of the desiccant approaches zero, however, the moisture contentof gas passed over it rises sharply. If moisture content, dewpoint orrelative humidity of the gas be measured, and plotted against time, thisusually sudden rise in moisture content is noted as a change in slope,and the increasing moisture content then rapidly approaches the moisturecontent of the influent gas. The resulting S-shaped portion of thiscurve in effect represents the moisture front, and if this be observedin terms of the length of the bed, it will be found to progress from theinfluent end to the effluent end of the bed as the adsorption cycleproceeds. The objective is to conclude the cycle before the front orchange in slope of the curve reaches the end of the bed, sincethereafter the rise is so rapid that delivery of undesirably moisteffluent can hardly be prevented.

As a further feature in accordance with the invention, the regenerationcycle need not be and in most cases is not of a duration equal to thedrying cycle, so that the application of microwave energy can bediscontinued when regeneration is complete, and the remainder of thetime can be used for any required cooling down of the regenerated bed,so that it is at a convenient and efficient temperature for adsorptionwhen the flow of influent gas to that bed is resumed.

The gas fractionating apparatus in accordance with the inventioncomprises a sorbent bed having a preferential affinity for a first polargas in a mixture thereof with a second gas and adapted for periodicregeneration at the conclusion of an adsorption cycle by removal ofsorbed first polar gas by application of microwave energy, with aflushing flow of purge gas to remove desorbed first polar gas from thebed, preferably in counterflow to flow during adsorption, and means forapplying microwave energy to the sorbent bed during such regeneration.

While the apparatus of the invention can be composed of one sorbent bed,the preferred system employs a pair of sorbent beds disposed inappropriate vessels, which are connected to the lines for reception ofinfluent gas to be dried, and delivery of effluent dried gas.

The apparatus can also include a check valve or throttling valve for thepurpose of reducing pressure during regeneration, and a multiple channelvalve for cycling the flow of influent gas between the beds and forreceiving the flow of effluent gas therefrom. In addition, a metering orthrottling valve can be included to divert a portion of the effluent gasas purge in counterflow through the bed being regenerated.

It is preferred, in accordance with the invention, to pass purge gas incounterflow to influent gas being dried, in accordance with the normalpractice of the art, to provide efficient flushing of desorbed firstpolar gas with minimum gas loss. It will, however, be understood that ifdesired the purge flow can be passed through the bed in the samedirection as the influent flow, with a corresponding loss in efficiency.

The microwave generator can be any capable of generating electromagneticwaves having frequencies within the range from about 0.03 to about 3000giga Hertz (equivalent to about 3×10⁷ to about 3×10¹² cycles persecond). Microwave generators of this capability are availablecommercially, and form no part of the invention. Microwave generatorsemploying amplitron, magnetron, microtron or klystron tubes aresuitable, but any type of microwave generating tube can of course beused. Exemplary microwave generators include Gerling Moore Model No.4003, Cober No. S6, Toshiba No. TMG-490 and Thomson No. TH3094.

The size and capacity of the microwave generator will of course beselected according to the regeneration requirements of the system. Wherethe regeneration requirements are exceptionally large, the size of thegenerator may be increased, or it may be possible simply to multiply thenumber of generators, and feed the microwave energy into the sorbent bedat several locations, one for each generator used. It is also possibleto use orthogonal mode transducers, to feed power from two or moregenerators into one sorbent bed, using only one opening.

The microwave generator is coupled with an isolator so as to protect thegenerator in the event of an operator error or other system fault.

In series between the isolator and the microwave generator is interposeda forward/reflect monitor, whose function is to shut off the microwavegenerator when the sorbent bed has been fully regenerated. While thereis free water or sorbed polar gas present on the sorbent or desiccant,the microwave energy transmitted into the sorbent bed will be absorbed.When the sorbed material has been desorbed, however, the absorption ofmicrowave energy drops appreciably, and the microwaves instead of beingabsorbed are reflected back through the microwave transmittal systemtowards the microwave generator. The interposition of theforward/reflect monitor before the generator makes it possible to detectthe reflected waves, and, at a predetermined intensity corresponding toregeneration of the sorbent, cut off the microwave generator. Theintensity of reflected waves corresponding to complete regeneration isof course determined by trial and error, for the particularadsorption/desorption system being used.

Any conventional forward/reflect monitor can be employed. These areavailable commercially, and form no part of the instant invention.Exemplary monitors include Gerling Moore No. 4009, and Cober 6 KWreflected power meter.

A single microwave generator, forward/reflect monitor and isolatorcombination is sufficient for an adsorption/desorption system having anynumber of sorbent beds. If there is more than one sorbent bed, however,it is necessary to provide separate microwave conducting systemstransmitting the microwave energy to each of the beds, with a waveguideswitch to divert the energy to the bed selected for regeneration. Thetransmittal system beyond the switch and before the sorbent includeswaveguide segments, microwave windows, and subtuners, all ofconventional design and forming no part of the instant invention.

The microwave windows must of course be transparent to the microwaveenergy used, must be capable of retaining the gas pressures within thesorbent bed, and are usually interposed at or in the walls of the vesselin which the sorbent bed is contained. Any microwave-transparentmaterial can be used for the construction of the windows.

The waveguide segments are in effect conduits capable of conductingmicrowave energy without loss to the atmosphere. Suitable waveguidesegments include Gerling Moore Nos. 4016 and 4017, and Cober No. WR284.

The microwave tuners employed in conjunction with the wave guidesegments and windows are impedance matching devices. Gerling Moore No.4027 is exemplary. Others include Microwave Fusion Model Tuner -S andWaveline Model 4360.

The gas fractionating system in accordance with the invention isillustrated in the drawings in the form of dryers, in which:

FIG. 1 is a schematic view of a two-bed two-tank dryer in accordancewith the invention; and

FIG. 2 is a schematic view of a two-bed dryer in accordance with theinvention, held within a single tank.

FIG. 2A is a schematic view of the microwave energy generating systemdesignated as "100" in FIG. 2.

The dryer shown in FIG. 1 is composed of a pair of tanks 10 and 11, eachhaving at their ends an inlet 2 and 3, and at the other end an outlet 4and 5. Disposed across the inlets and outlets of each are stainlesssteel support screens 6, made of wire mesh or perforated steel plate,the purpose of which is to retain the desiccant particles within thetanks under gas flow in either direction, and to prevent thetransmission of microwave energy either upstream or downstream.

In this case, the tanks are filled with desiccant, activated alumina,but optionally a molecular sieve such as Na₁₂ [AlO₂)₁₂ (SiO₂)₁₂ ]3H₂ Oor a silica gel can be used.

The tanks 10 and 11 are interconnected by a system of lines to ensuredelivery of influent gas to be dried to the inlet of either bed, and thewithdrawal of dried gas from the outlet of either bed, with lines fordirecting purge flow bled off from the effluent to the top of either bedfor regeneration, and to vent it to atmosphere after leaving the bottomof each bed. This system is composed of a wet gas delivery line 20,which conducts wet gas to the four-way switching valve 21, and thenthrough either line 22 or 23 to the top of tanks 10 and 11,respectively. Similar line connections 24 and 25 extend between theoutlets of the two tanks. Flow along these lines to outlet line 26 iscontrolled by the check valves 27 and 28. Another line 29 interconnectslines 24 and 25 via a purge-metering and pressure-reducing orifice 30,which controls the volume of purge flow bled from the dry gas effluentfor regeneration of the dryer bed on the regeneration cycle. The line 29leads the purge flow through the orifice 30 to the outlets 4 and 5 oftanks 10 and 11. A purge exhaust line 36 interconnects lines 22 and 23via exhaust valves 34,35 to vent purge to atmosphere via the vent line37 and muffler 38.

The apparatus for developing and applying microwave energy to thesorbent bed in each tank for regeneration is disposed intermediate thetwo tanks, and is composed of a microwave generator 40, aforward/reflect monitor 41, a microwave isolator 42, and a waveguideswitch 43, which directs the microwave energy through one of the twosets of waveguides 44, 45, microwave tuners 46,47 and microwave pressurewindows 48,49, through which the microwave energy passes via thetransition sections 50, 51 into the sorbent in one of the two tanks 10,11 respectively.

Each tank 10, 11 also carries a temperature switch 52,53.

If tank 10 is on the drying cycle, and tank 11 on the regeneratingcycle, then operation of the dryer is as follows: Wet gas at linepressure 25 to 350 psig entering through line 20 is diverted by valve 21into line 22 to tank 10, and passes thence downwardly through the bed 9to the outlet, whence it is conducted via line 24 past the open valve 27to the exhaust line 26. Valves 28 and 34 are closed, preventing flow inline 25 from line 24 except via line 29 and orifice 30, and in line 36from line 22, while valve 35 is open, permitting purge flow from tank 11to proceed to vent line 37. A portion of the effluent is then passedthrough line 29, through orifice 30, where its pressure is reduced toatmospheric, due to open line 37, into line 25 to the bottom 5 of thesecond tank 11, which is on the regeneration cycle, and it passes thenceupwardly through the bed 9 to the inlet 3 and thence through the line 36and is vented to the atmosphere through the purge exhaust line 37 andmuffler 38.

While this is going on, microwave energy is being produced in themicrowave generator 40, and directed through the forward/reflect monitor41 and isolator 42 into the switching device 43, where the microwavesare directed into the tank 11 through the microwave guide 45, microwavetuner 47, pressure window 49, and transition section 51. The microwaveenergy is absorbed by the water held in the desiccant, and the water isdriven off as water vapor.

The purge gas flow is metered and reduced in pressure through theorifice 30, passes via lines 29 and 25 into the tank 11 at the outlet 5,and sweeps the desorbed water vapor out of the tank 11 through the inlet3 and past the exhaust valve 35 in line 36 to the vent line 37 and themuffler 38, where it is vented to the atmosphere. When all of the wateris driven out of the tank 11, a large percentage of the microwave energywill be reflected back through the waveguide 51 towards the microwavegenerator 40. The inlet and outlet screens 6 will prevent the energyfrom exiting in any other direction in the monitor 41 will sense thehigh percentage of reflected energy, and will shut off the microwavegenerator 40. The high temperature switch 53 serves as a back-up, toshut off the microwave generator in the event of a monitor malfunction.

When the predetermined cycle time has elapsed, an electric switch isactivated, which first closes valve 35 to permit repressurization of thetank 11. At the end of a predetermined time period, allowing sufficienttime for repressurization of tank 11, a motor is actuated to rotate thefour-way switching valve 21 through 180°, so as to divert influent gasto line 23 to the top of the second tank 11 on the drying cycle, whileat the same time the valves 27 and 35 are closed, and the valve 28 isopened. Valve 34 is now opened to depressurize tank 10 and open thepurge system to atmosphere. Purge flow now passes through line 29,orifice 30 and line 24 to the bottom 4 of the tank 10, which is now onthe regeneration cycle. At the time valve 21 is switched the microwavegenerator 40 is turned on, and the microwaves that are generated aredirected through the forward/reflect monitor 41 and isolator 42 into theswitching device 43. The switching device now directs the microwavesinto the tank 10, through the microwave guide 44, microwave tuner 46,pressure window 48, and transition section 50, into the sorbent bed 9.The microwave energy is absorbed by the free water sorbed on thedesiccant 9 in the tank 10, and the water is driven off as water vapor.The purge gas, proceeding via orifice 30, lines 29 and 24 into thebottom of the tank 10, sweeps the desorbed water vapor out of the tank10 through the inlet 2, exhaust valve 34, lines 36 and 37, and muffler38 into the atmosphere.

When all of the water is driven out of the tank 10, a large percentageof the energy will be reflected back through the waveguide towards themicrowave generator. The inlet and outlet screens 6 will prevent theenergy from exiting in any other direction. The monitor 41 will thensense the high percentage of reflected energy, and will automaticallyshut off the generator. The high temperature switch 52 serves as aback-up, to shut off the generator in the event of a monitormalfunctioning. Then the valves 21,27,28,34 and 35 are again switched atthe end of the predetermined drying period, and the cycle is repeated.

Whenever the tank 10 or 11 is on the regeneration cycle, the microwavegenerator 40 is activated, and the desiccant bed is desorbed while beingsubjected to the purge flow for the time required to fully regeneratethe desiccant. This time may be considerably less than the drying cycletime, which of course is determined not by a fixed time cycle, but bythe moisture level in the gas in the bed as noted previously, whereuponthe microwave generator is shut off.

Purge flow of gas is continued only for a time sufficient to cool thedesiccant bed to room temperature, at which temperature the adsorptionis more efficient, and then it too is automatically shut off by closingpurge exhaust valves 34 and 35, repressurizing the spent bed, andreadying it for the next cycle. Normally, from a half-hour to one houris adequate to effect complete regeneration of a spent bed, and from 1/2to 1 hour is enough to cool it. However, other times can of course beused, depending upon the desiccant that is employed.

The single tank dryer shown in FIG. 2 is composed of a single tank shell60 within which is disposed a central barrier 61 separating the tankinto two chambers 62 and 63, each having at one end an inlet 64 and 65and at the other end an outlet 66 and 67. Disposed across the outlets ofeach are stainless steel support screens 68 made of wire mesh orperforated steel plate, the purpose of which is to retain the desiccantparticles within the tanks, and to prevent transmission of microwaveenergy either upstream or downstream.

The tanks are filled with desiccant 9, such as activated alumina.

The chambers 62, 63 are interconnected by a system of lines, to ensuredelivery of influent gas to be dried to the inlet of either bed, and thewithdrawal of dried gas from the outlet of either bed, with lines fordirecting purge flow bled off from the effluent to the top of either bedfor regeneration, and to vent it to atmosphere after leaving the bottomof each bed. This system is composed of a wet gas delivery line 80,which conducts wet gas to the four-way switching valve 81, and thenthrough either line 82 or 83 to the top of chambers 62 and 63,respectively. Similar line connections 84 and 85 extend between theoutlets of the two chambers. Flow along these lines to outlet line 86 iscontrolled by the switching valves 87 and 88. Another line 89 leads fromthe junction of lines 84 and 85 to a purge-metering valve 90, whichcontrols the volume of purge flow bled from the dry gas effluent forregeneration of the dryer bed of the regeneration cycle. The line 89leads the purge flow through pressure-reducing orifice 72 to one oflines 73, 74 and check valves 75 and 76, and to the outlets 66 and 67 ofchambers 62 and 63. A purge exhaust line 92 leads from the four-wayvalve 81 past purge exhaust valve 91, to vent purge to atmosphere.

Disposed at the base of the tank 60 is a microwave energy generatingsystem composed of a microwave generator 100 from which the microwaveenergy is directed through a forward/reflect monitor 101 and an isolator102 into a switching device 103. The switching device directs themicrowaves into the off-stream chamber, either 62 or 63, throughmicrowave guides 104, 105, microwave tuners 106, 107, pressure windows108, 109 and transition sections 110, 111. The microwave energy isabsorbed by free water sorbed onto the desiccant, and the water isflushed out as water vapor by the purge gas past the purge exhaust valve91, venting the purge to atmosphere. The inlet and outlet screens 68prevent the energy from exiting except back through the waveguidestowards the microwave generator. The forward/reflect monitor 101 willsense the high percentage of reflected energy present in the chamberwhen all of the water has been driven out, and will thereupon shut offthe microwave generator 100. The high temperature switches 112, 113serve as a backup, to shut off the generator 100 in the event of amonitor malfunction.

If chamber 62 is on the drying cycle, and tank 63 on the regeneratingcycle, then operation of the dryer is as follows: Wet gas at linepressure, 25 to 350 psig, entering through line 80, is diverted by valve81 into line 82 to chamber 62, and passes thence downwardly through thelayer 78 to the outlet, whence it is conducted via line 84 past the openvalve 87 to the exhaust line 86. Valves 88 and 75 are closed, preventingflow in lines 85 and 73, respectively. A portion of the effluent, ascontrolled by the purge valve 90, is then passed through line 89,through orifice 72, where its pressure is reduced to atmospheric, due toopen purge valve 90, into line 74, past open valve 76 (valve 75 isclosed, preventing flow in line 73) to the bottom of the second chamber63, which is on the regeneration cycle, and it passes thence upwardlythrough the bed to the inlet 65 and thence through the line 83 to thefour-way switching valve 81, and is vented to the atmosphere through thepurge exhaust line 92 and valve 91.

While this is going on, microwave energy is being produced in themicrowave generator 100, and directed through the forward/reflectmonitor 101 and isolator 102 into the switching device 103, where themicrowaves are directed into the chamber 63 through the microwave guide105, microwave tuner 107, pressure window 109, and transition section111. The microwave energy is absorbed by the water held in thedesiccant, and the water is driven off as water vapor.

The purge gas flow is metered through the valve 70 and reduced inpressure through the orifice 72, passes via lines 89, 74, into thechamber 63 at the outlet 67, sweeps the desorbed water vapor out of thechamber 63 and via exhaust line 92 past the exhaust valve 91 and themuffler 98, where it is vented to the atmosphere. When all of the wateris driven out of the chamber 63, a large percentage of the microwaveenergy will be reflected back through the waveguide 105 towards themicrowave generator 100. The inlet and outlet screens 68 will preventthe energy from exiting in any other direction. The monitor 101 willsense the high percentage of reflected energy, and will shut off themicrowave generator 100. The high temperature switch 113 serves as aback-up, to shut off the microwave generator in the event of a monitormalfunction.

When the predetermined cycle time has elapsed, an electric switch isactivated, which first closes purge exhaust valve 91, to repressurizethe chamber 63, and then about 30 seconds later switches the four-wayswitching valve 81 through 180°, so as to divert influent gas to line 83to the top of the second chamber 63 on the drying cycle, while at thesame time the valves 87 and 76 are closed, and the valves 75, 88 and 91opened. Purge flow now passes through line 89, orifice 72 and line 73past valve 75 to the bottom 66 of the chamber 62, which is now on theregeneration cycle. At the time valve 81 is switched the microwavegenerator 100 is turned on, and the microwaves that are generated aredirected through the forward/reflect monitor 101 and isolator 102 intothe switching device 103. The switching device now directs themicrowaves into chamber 62, through the microwave guide 104, microwavetuner 106, pressure window 108, and transition section 110, into thesorbent bed 9. The microwave energy is absorbed by the free water sorbedon the desiccant 9 in the tank chamber 62, and the water is driven offas water vapor. The purge gas proceeding via valve 90, orifice 72,through lines 89, 73 into the bottom of the chamber 62 sweeps thedesorbed water vapor out of the chamber through the line 82 and valve81, and thence into the atmosphere via line 91 and valve 92.

When all of the water is driven out of the chamber 62, a largepercentage of the energy will be reflected back through the waveguidetowards the microwave generator. The inlet and outlet screens 68 willprevent the energy from exiting in any other direction. The monitor 101will then sense the high percentage of reflected energy, and willautomatically shut off the generator 100. The high temperature switch112 serves as a back-up, to shut off the generator in the event of amonitor malfunction. Then valves 81,87,88,75 and 76 are again switchedat the end of the predetermined drying period and the cycle is repeated.

Whenever the chamber 72 or 92 is on the regeneration cycle, themicrowave generator 100 is activated, and the desiccant bed is desorbed,while being subjected to the purge flow for the time required to fullyregenerate the desiccant. This time may be considerably less than thedrying cycle time, which of course is determined not by a fixed timecycle but by the moisture level in the gas in the bed, as notedpreviously, whereupon the microwave generator is turned off.

Purge flow of gas is continued only for a time sufficient to cool thedesiccant bed to room temperature, at which temperature the adsorptionis more efficient, and then it too is automatically shut off by closingpurge exhaust valve 91, repressurizing the spent bed, and readying itfor the next cycle. Normally, from a half-hour to one hour is adequateto effect complete regeneration of a spent bed, and from 1/2 to 1 houris enough to cool it. However, other times can of course be used,depending upon the desiccant that is employed.

The process of the invention can be carried out utilizing any type ofdesiccant or sorbent that is transparent to microwave energy. Suchdesiccants and sorbents exhibit transparency only at relatively lowtemperatures. At elevated temperatures of 2000° to 3000° F. and above,most desiccants or sorbents are not transparent to microwave energy. Atlow temperatures, below 500° F., all are transparent. Between 500° and2000° F., transparency is lost by many desiccants and sorbents.Consequently, the process of the invention is carried out at atemperature at which the sorbent or desiccant is transparent, andpreferably below 500° F.

The desiccant or sorbent is preferably one having strongly bond water ofhydration, such as molecular sieves or alumina. Also exemplary aresilica gel, Mobil Sorbeads, magnesium sulfate, calcium sulfate,zeolites, both natural and synthetic such as chabasites, analcite, andthe synthetic zeolites described in U.S. Pat. Nos. 2,306,610, 2,442,191and 2,522,426.

The adsorption can be carried out at atmospheric pressure. However,since the rate and extent of adsorption increases with pressure, it isusually preferred that it be carried out at a superatmospheric pressure,generally from about 30 to about 10,000 psig. On the other hand,regeneration proceeds more efficiently and effectively at a reducedpressure, and thus it would be preferable in most instances to use areduced pressure during this portion of the cycle. If the adsorption iscarried out at a superatmospheric pressure, then regeneration isconveniently carried out at atmospheric or below atmospheric pressure,say, at 0.1 to 10 psi, such as by application of a vacuum pump, waterpump, or steam ejector.

The flow rate will be determined according to system requirements. Thefaster the flow, the more frequent the cycling and/or the larger thevolume of desiccant required. Flow rates up to 8000 scfm are readilyaccommodated without loss of effectiveness, with most desiccants.

The regeneration of the spent desiccant in accordance with the inventionis effectively brought to completion by the use of microwave energy. Theamount of energy applied is sufficient to remove substantially all ofthe adsorbed moisture, for maximum efficiency of operation. Of course,if maximum efficiency is unnecessary, then the regeneration need not becarried as far as substantially complete regeneration. However, inasmuchas the efficiency of adsorption decreases as the adsorbent takes upmoisture, it is obviously more desirable in nearly every instance tocompletely regenerate, if possible.

It will of course be understood that the term "complete regeneration" isused in its normal sense. It is, of course, impossible to ever removeall of the moisture content of an adsorbent, even by long continuedapplication of microwave energy.

The dryer size and operating conditions required for a given wet gasare, of course, readily determined by those skilled in the art. Thevariables to be controlled include the frequency and intensity ofmicrowave energy applied, the volume of desiccant, the time for theregenerating cycle, and the moisture content of the desiccant reachedduring the drying cycle. The following computation will be exemplary.

Let it be assumed that the system provides two tank chambers having aninternal diameter of 12 inches and a total length of 51 inches effectivebed length, giving a volume of 3.34 cubic feet for a desiccant bed ineach tank. Let it be further assumed that a bed of activated alumina beprovided.

The influent flow proceeds towards the bottom of the bed through thealumina, and the purge counterflow proceeds from the effluent end.

It is customary to design a heat regenerated dryer on the basis that thetotal moisture content of the influent air during the drying period,assuming rated flow of saturated air, is less than 5% of the weight ofthe desiccant in the bed. To rephrase this criterion, it is assumed thatvirtually all the water is adsorbed by the influent one-third of the bedand the average water content of this part of the bed is 15% by weight.

In this case, one-third of the bed is one-third of 3.34 or 1.11 cubicfeet. The desiccant weight in this portion of the bed is 54.5 lbs. andthe weight of water to be collected is 15% of 54.5 lbs. or 8.2 lbs.

It is further customarily assumed in calculations that the maximum airinlet temperature is 100° F. unless more accurate data is available fora given application. In this case, saturated air at 100° F. will contain0.00279 lb. of moisture per cubic foot. Thus, for a one hour dryingcycle, this bed can handle a flow rate of:

    8.2/(60×0.00279)=49 cfm

If the inlet pressure is 100 psig, the inlet flow rate can be:

    49×(114.7/14.7)=382 scfm

It is thus evident from this computation that such a bed has a very highflow rate capacity.

The computation of the purge flow for such a bed would be as follows:For a 56 minutes regeneration cycle, allowing 2 minutes fordepressurization, 2 minutes for repressurization, and 2 minutes' delaybefore switching the beds, there would be a lost regeneration time of 6minutes, of a total cycle time of 56 minutes. The microwave generatorcan be operated during depressurization so that time is not lost, andthe actual time lost is only 4 minutes.

During the remaining 52 minutes of the cycle, the bed is heated up andthen cooled off. Only about 1/2 of the time period will be effective forregeneration so the purge flow must be capable of carrying off 8.2 lbs.of moisture in 26 minutes with an outlet gas temperature of 204° F.,assuming the gas is only 80% efficient in taking moisture from thedesiccant and therefore has a relative humidity of 80%. Under theseconditions, each cubic foot of purge gas will hold:

    0.80×0.213=0.170 lb of moisture

The purge flow must then be:

    8.2/(0.170×26)=1.9 scfm

Based on 380 scfm inlet flow, a 1.9 scfm purge is about 1/2% of theinlet flow.

The heat requirements are computed as follows:

The weight of desiccant in the heated portion of the bed is 64 lbs. Theheat needed to heat this weight of desiccant to 200° from 100° F. is

    64×100×0.25=1,600 B.t.u.

The heat required to desorb 8.2 lbs. of water is:

    8.2×1450=11,890 B.t.u.

The bed can be adequately cooled in 26 minutes, leaving 26 minutes forheating time.

The heat required to warm the purge gas from 100° F. to 204° F. duringthe heating period is:

    1.9×0.075×0.25×104×26=96 B.t.u.

The total heat requirements, allowing about 5% for heat losses, are then14,265 B.t.u. In order to provide this amount of heat in 26 minutes, atotal of:

    (14,265/3414)×(60/26)=9.64 kilowatts

of heating capacity must be provided.

If the entire bed were to be heated to 300° F. as in a conventional unitand the time cycle held, the heat required to heat the entire desiccantbed (192 lbs.) from 100° F. to 300° F. would be 9600 B.t.u. This amountof heat could not be carried off in 26 minutes by 1.9 scfm of purge gasso the purge would have to be increased to about 60 scfm. The heatingperiod is 26 minutes and the heat required to heat the purge gasbecomes:

    60×0.075×0.25×200×26=5850 B.t.u.

The total heat requirement, allowing 10% for heat losses due to thehigher temperature, is now about 30,100 B.t.u., an increase of 111%.Further, the heaters must now have a heating capacity of:

    (30,100/3414)×(60/26)=20.4 kilowatts

an increase of 111%.

These larger heaters greatly increase manufacturing cost and theadditional power required for regeneration greatly increases operatingcost.

It is of course possible to provide a fully heated dryer containing 192lbs. of desiccant in each tank with smaller heaters, such as 10.4kilowatts. Under these circumstances, the cycle time must be lengthenedto provide longer heating and cooling periods, and the influent flowrating must be reduced proportionately to avoid over-saturating the bed.Thus, the same size dryer operated on a two hour drying cycle could use10.4 kilowatt heaters, but would have to be rated for only 190 scfm, adecrease of 50% in capacity.

The dryers in accordance with the invention can be used for drying gasesof all types, such as for drying small flows of compressed gases ininstrument air, inert gas, and purge systems to dry relatively largevolumes of compressed air or gas for industrial and laboratory purposes,and also of relatively large capacity to provide air or gases havingsub-zero dewpoints.

The volume of desiccant bed required will be sufficient to provide inthe heated portion of the bed the capacity needed for normal operation.There will also have to be provided a sufficient volume of reserve bedwithout heater units to meet any emergency requirement due to temporaryoverloading of the equipment, due to the supplying of a gas of anunusually high moisture content, or due to the supplying of the gas at ahigher flow rate.

The drying systems in accordance with the invention can include moistureindicators and moisture control systems of various types to measure theeffluent flow and to control the cycling between the spent andregenerated beds. Desiccant drain and fill ports can be provided tofacilitate servicing of the desiccant, and outlet filters also can besupplied to prevent carryover of desiccant particles from the bed intoother parts of the system.

In operation, the dryers of the invention will provide gas of lowmoisture content at considerably lesser operating cost than aconventional heat reactivated dryer. The reduction in heating capacityalso reduces the time required for cooling of the bed, and the purge gasrequirement can also be reduced, as compared to a conventional dryer.

While the invention has been described with principal emphasis on adesiccant dryer and a process for drying gases, it will be apparent tothose skilled in the art that this apparatus with a suitable choice ofadsorbent can be used for the adsorption of one or more polar gaseouscomponents from a gaseous mixture with other polar and/or nonpolargases. In such a case, the adsorbed polar component can also be removedfrom the sorbent by application of microwave energy and optionally, inaddition, a reduction in pressure during regeneration. Thus, the processcan be used for the separation of moisture and/or ozone and/or carbondioxide or carbon monoxide from petroleum hydrocarbon streams and othergas mixtures containing the same, for the separation of moisture and/orozone and/or carbon dioxide or carbon monoxide from nitrogen, for theseparation of moisture and/or ozone and/or carbon dioxide or carbonmonoxide from saturated hydrocarbons, and the like. Those skilled in theart are aware of sorbents which can be used for this purpose.

In many cases, sorbents useful for the removal of moisture from air canalso be used, preferentially to adsorb one or more polar gas componentsfrom a mixture thereof, such as activated carbon, glass wool, adsorbentcotton, metal oxides and clays such as attapulgite and bentonite,fuller's earth, bone char and natural and synthetic zeolites. Theselectivity of a zeolite is dependent upon the pore size of thematerial. The available literature shows the selective adsorptivity ofthe available zeolites, so that the selection of a material for aparticular purpose is rather simple, and forms no part of the instantinvention.

In some cases, the adsorbent can be used to separate a plurality ofmaterials in a single pass. Activated alumina, for example, will adsorbpolar gases such as water vapor, carbon dioxide, and ethanol vapor, incontrast to Mobil Sorbeads, which will adsorb only water vapor in such amixture.

The apparatus employed for this purpose will be the same as thatdescribed and shown in FIGS. 1 and 2, inclusive, and the process is alsoas described, suitably modified according to the proportions of thecomponents to be separated, the operating pressure and temperature, andthe volume of available sorbent.

It will, however, be understood that the process is of particularapplication in the drying of gases, and that this is the preferredembodiment of the invention.

The following Example in the opinion of the inventors represents apreferred method of operation of a dryer system in accordance with theinvention.

EXAMPLE 1

A two bed microwave-energy reactivatable dryer of the type shown in FIG.1, having two desiccant beds 48 inches long, containing 150 lbs. ofactivated alumina, was used to dry atmospheric air of 90% to 100%relative humidity at 100° F. to 70° F. at 90 psig inlet pressure. Thesuperficial flow velocity of the air was 47 cubic feet per minute, andinlet flow as 380 scfm, and the drying cycle was one hour, allowing twominutes for depressurization, two minutes for repressurization, and twominutes' delay for switching the beds. The microwave generator wasoperated during depressurization, and during regeneration thetemperature of the outlet purge gas was 160° F. and relative humidity80%. Purge flow as 1.9 scfm, regeneration time was 30 minutes, andcooling time 30 minutes.

It was apparent from the data for a large number of runs that in eachrun the microwave generation system had substantially fully regeneratedthe bed by the time the cycle was terminated at a safe moisture level inthe effluent gas. It was also clear from the different times of thecycle that it was possible to adjust cycle length to match variation inmoisture level of the influent air, and thus preserve desiccant life bycutting down the number of regenerations materially, without affectingappreciably the completeness of the regeneration.

Having regard to the foregoing disclosure, the following is claimed asthe inventive and patentable embodiments thereof:
 1. In the process forremoving a first polar gas from a mixture thereof with a second gas byflow of the gas mixture continuously through a stationary sorbent bedhaving a preferential affinity for the first polar gas which includesthe steps of passing the gas mixture in contact with and from one end toanother end of a first bed of the sorbent; sorbing first polar gasthereon and, as the sorption of the first polar gas continues, forming aconcentration gradient of first polar gas in the first bed progressivelydecreasing from one end to the other end of the bed ranging from asubstantial proportion of the first sorbent capacity therefor at one endto less than 20% of its capacity therefor at the other end, so as toproduce a gaseous effluent which has a concentration of the first polargas therein below a predetermined maximum; removing first polar gassorbed on the second sorbent bed by passing a purge flow of effluent gasin contact with the sorbent bed, discontinuing the purge flow, and thenresuming passing the gas mixture in contact with the sorbent bed, theimprovement which consists essentially in utilizing a sorbenttransparent to microwave energy having a frequency within the range ofabout 0.03 to about 3000 giga Hertz, and desorbing first polar gas byapplying during the purge flow microwave energy having a frequencywithin the range of about 0.03 to about 3000 giga Hertz at a temperatureat which the sorbent is transparent to microwave energy, the microwaveenergy being preferentially absorbed by the first polar gas sorbed onthe sorbent, and this gas thereby being desorbed, and haltingapplication of the microwave energy when desorption of first polar gasis substantially complete, and before water of hydration of the sorbentis removed.
 2. A process according to claim 1 in which the applicationof microwave energy is at a temperature below about 500° F.
 3. A processaccording to claim 2 in which the sorbent is a desiccant.
 4. A processaccording to claim 1 in which the sorbed material is water.
 5. A processaccording to claim 4 in which the sorbent is a molecular sieve.
 6. Aprocess according to claim 4 in which the sorbent is alumina.
 7. Aprocess according to claim 4 in which the sorbent is silica gel.
 8. Aprocess according to claim 1 in which the purge gas is at effluent gastemperature and is not heated.
 9. A process for reducing theconcentration of a first polar gas in a mixture thereof with a secondgas to below a limiting maximum concentration thereof in the second gas,which consists essentially in passing the mixture in contact with andfrom one end to another of a stationary bed of a sorbent having apreferential affinity for the first polar gas, and transparent tomicrowave energy having a frequency within the range of about 0.03 toabout 3000 giga Hertz; adsorbing first polar gas thereon to form agaseous effluent having a concentration thereof below the maximum, andas the adsorption continues forming a concentration gradient of firstpolar gas on the bed progressively decreasing from the one end to theother end, and an increasing concentration of first polar gas in thesecond gas defining a concentration front progressively advancing in thebed from the one end to the other end as sorbent capacity therefordecreases; discontinuing passing the gaseous mixture in contact with thebed before the front can leave the bed, and the limiting maximumconcentration of first polar gas in the second gas can be exceeded; andthen desorbing the first polar gas adsorbed on the sorbent bed byapplication of microwave energy having a frequency within the range ofabout 0.03 to about 3000 giga Hertz at a temperature at which thesorbent is transparent to microwave energy while passing therethrough apurge gas flow to flush desorbed first polar gas from the bed.
 10. Aprocess according to claim 9 in which the application of microwaveenergy is at a temperature below about 500° F.
 11. A process accordingto claim 9 in which purge gas is gaseous effluent from the adsorption.12. A process according to claim 9 in which the desorption is at a gaspressure lower than that during adsorption.
 13. A process according toclaim 9 in which the desorption is of a duration less than the sorption,and application of microwave energy is discontinued when desorption issubstantially complete.
 14. A process according to claim 9 in which atleast two sorbent beds are used, and adsorption is carried on in onesorbent bed while another sorbent bed is being desorbed, so thatadsorption is continuous and always in progress in at least one of thesorbent beds.
 15. A process in accordance with claim 9 in which thefirst polar gas is water vapor.
 16. A process in accordance with claim 9in which the sorbent is silica gel.
 17. A process in accordance withclaim 9 wherein the purge flow is of effluent gas from the bed sorbingthe first polar gas.
 18. A process in accordance with claim 9 whichcomprises removing sorbed first polar gas at a reduced pressure relativeto the pressure of adsorption.
 19. An apparatus for reducing theconcentration of a first polar gas in a mixture thereof with a secondgas to below a limiting maximum concentration thereof comprising, incombination, a stationary bed of sorbent having a preferential affinityfor the first polar gas; and transparent to microwave energy having afrequency within the range of about 0.03 to about 3000 giga Hertz; aninlet line for delivering influent gas at an inlet end of the bed; andan outlet line for delivering effluent gas from an outlet end of thebed; means for applying to the sorbent bed microwave energy having afrequency within the range of about 0.03 to about 3000 giga Hertz fordesorbing first polar gas from the bed at the conclusion of anadsorption cycle; and means for supplying a flushing flow of purge gasduring application of microwave energy to remove desorbed first polargas from the bed.
 20. An apparatus according to claim 19 comprising atleast two sorbent beds disposed in separate chambers and connected tothe lines for reception of influent gas to be dried, and for delivery ofeffluent gas; and at least one valve for cycling the flow of influentgas to one of the beds at a time, and for receiving the flow of effluentgas from one of the beds at a time.
 21. An apparatus according to claim20 comprising a pressure-reducing valve for reducing pressure duringdesorption.
 22. An apparatus according to claim 20 comprising a valve todivert a portion of the dried effluent gas as purge through the bedbeing desorbed.
 23. An apparatus according to claim 20 comprising avalve to divert a portion of the dried effluent gas as purge incounterflow through the bed being desorbed.
 24. An apparatus accordingto claim 19 in which the microwave generator comprises a magnetron tubeas a source of microwave energy.
 25. An apparatus according to claim 19in which the microwave generator comprises a amplitron tube as a sourceof microwave energy.